Diquaternary salts of di-4-pyridyl ketone

ABSTRACT

New compounds which are bis aryl ketones where the aryl group contains nitrogen or nitrogen and sulfur, which are useful in chemiluminescent compositions.

nited States Patent Maulding June 28, 1974 DIQUATERNARY SALTS OF DI-4-PYRIDYL KETONE [75] Inventor: Donald Roy Maulding, Branchburg,

Township, Somerest Cty., NJ.

[73] Assignee: American Cyanamid Company,

Stamford, Conn.

[22] Filed: Dec. 7, 1972 [21] Appl. No.: 313,028

[58] Field of Search 260/294.8 R, 295 AM, 296

[56] References Cited UNITED STATES PATENTS 3,206,383 9/1965 Kappel 260/297 R Primary Examiner-Alan L. Rotman Attorney, Agent, or Firm-Charles Joseph Fickey 5 7] ABSTRACT New compounds which are bis aryl ketones where the aryl group contains nitrogen or nitrogen and sulfur, which are useful in chemiluminescent compositions.

5 Claims, N0 Drawings 1 DIQUAIER MELSALIQQFPHXYBEYL KETONE The new compounds of the present invention have the general structural formula where represents anitrogen or nitrogen and sulfur containing aryl group, as exemplified by compounds of the following structures:-

where R=H or alkyl (of up to 8 or more carbon atoms), and X=Cl Br, I,

useful as dyes or in color imaging applications, and in chemiluminescent compositions.

Ultraviolet irradiation of the dimethochloride (R=CH X=Cl) in methanol or isopropanol gave a bright red color. The red solution immediately became deep blue when dilute alkali was added. When dilute base was added to a solution of the dimethochloride in isopropanol without prior irradiation, a deep blue color.

fonned, but not instantaneously. That the methyl groups in the dimethochloride had an effect on the formation of the red color was shown by irradiation of the dihydrochloride (R=H, X=Cl). At room temperature a pink color was produced, but at 77K a deep red color developed, which slowly faded when warmed to room temperature.

The dimethochlorides R=CH X=I; R=CH X= and the dihydrochloride (R=H, X =Cl) were found to be chemiluminescent when reacted with hydrogen peroxide in the presence of a flourescer, e.g. 9,l0-bis(- phenylethynyl)-anthrancene, and an organic solvent. Other suitable flourescers and solvents are disclosed in US. Pat. No. 3,576,987.

The following specific examples are set forth to illustrate the invention and are not intended to be limita- 0 vtive.

EXAMPLE I Di-4-pyridyl Ketone The dipyridyl ketone was prepared from 4-brom0pyridine, n-butyl lithium and 4- cyanopyridine according to the procedure described by J. P. Wilbant and L. G. Herringa, Rec. Trav. Chim., 74,

EXAMPLE ll Di-4-Pyridyl Ketone Dihydrochloride Monohydrate Anhydrous hydrogen chloride was bubbled into a solution of 0.5 g. of di-4-pyridyl ketone in 20 ml. of anhydrous methanol until no more precipitate formed. The yield of the white solid, mp, 258260 was 0.6l

g., or 88%.

Anal. CalCd. fOI' CuHmNgOgClzI C, H, C], 25.8; N, 10.2.

Found: C, 47.9; H, 4.5; Ci, 25.8; N, 9.8.

EXAMPLE lIl 4,4'-Carbonylbis[ l,methylpyridinium iodide 1- Monohydrate A mixture of 0.37 g. [12 mole] of methyl iodide in 20 ml. of absolute methanol was heated at in a 100 ml. stainless steel autoclave for 7 hours. Evaporation of the volatile material yielded a black gum, which became a brown solid, wt. 0.82 g., 89%, when heated in refluxing acetone. Recrystallization of 20 mg. from ml. of acetone yielded a redorange solid, mp, 253255 [dec.]; infrared, 2.90, 5.91 and 608 u.

Anal. Calcd. for C H l N O C, 32.1; H, 3.3; l, 52.2.

Found: C, 32.7; H, 3.2; I, 51.9.

A 47% yield of the monohydrate was obtained when 0.37 g. of ketone and 1.69 g. of methyl iodide were heated under nitrogen in 25 ml. of absolute methanol for 5 hours.

EXAMPLE lV 4,4'-Carbonylbis[l-methylpyridinium chloride]Diand Trihydrate The dimethochloride was prepared by dissolving the dimethiodide in water and passing the solution through a column packed with Dowex-l-X, ion-exchange resin. Evaporation of the water gave a gum. which became a maroon solid, mp, 13014l when heated in refluxing acetonitrile. A light pink solid, mp, 190-l93 was formed when the maroon product was heated in boiling isopropanol. The melting point was changed to 184.5-l 87.5 when the light pink solid was dried over phosphorus pentoxide at l /0.3 mm. Exposure to air caused the melting point to revert to l90-193.

Anal. Calcd. for C H Cl N O [m.p., l90-193]: C, 46.1; H, 5.9; Cl, 20.9; N, 8.3.

Found: C, 46.6; H, 5.3; Cl, 21.6; N, 8.8.

EXAMPLE V 4,4'-Carbonyl bis[ l-methylpyridinium tosylate] A slurry of 0.5 g. of di-4-pyridyl ketone and 1.8 g. of methyl p-toluenesulfonate was heated in a closed flask on a steam bath for 5-6 min. All the solid dissolved in the purple solution. Cooling gave a precipitate which was washed with benzene. The hygroscopic material.

was dried over P 0 at 1 10 (03 mm) for 5 hours. The melting point of the dried material was 135-l40.

Irradiation of the solutions of the solid in isopropanol with a GE. BH-6 lamp (Pyrex filter) gave pink solutlons.

EXAMPLE Vl Irradiation of Di-4-pyridyl Ketone Dihydrochloride Monohydrate A solution of 0.26 g. (0.001 mole) of the dihydrochloride. 50 ml. of methanol and 125 ml. of isopropanol while under nitrogen was irradiated with a GE. BH-6 lamp (Pyrex filter) for 4 /2 hours. A faint red color appeared. A deep red color appeared when a 3 ml. aliquot was irradiated at 77K, and slowly faded at room temperature.

EX MPL EXAMPLE Vlll Chemiluminescence of Diquaternary Salts of Di-4- pyridyl Ketone Visible emission was observed in a dark room by adding 3 ml. of 1.0 M H 0 in 3-methyl- 3-pentanol to a solution of 25-50 mg. of diquaternary salt and 3-5 mg. of 9.l0-bis(phenylethynyl)enthracene in 10 ml. of dibutyl phthalate. The intensity of emission was compared with the intensity of a luminol system: Compound lll gave brief and weak emission in an aqueous solution of H 0 and the sodium salt of fluorcscein.

Compound Intenslty i R-N c R C it it I. R=H, x=o1 Weak. 1r. R=0H,, x=r D0.

Medium. III. 11:0113, x=on;@soa

I claim: 1. A compound of the formula wherein A is N-R,

R is H, or lower alkyl, X is chloro, bromo, iodo or iodide) 

2. Di-4-pyridyl ketone dihydrochloride monohydrate as in claim
 3. 4,4''-carbonylbis(1-methylpyridinium iodide) monohydrate as in claim
 1. 4. 4,4''-carbonylbis(1-methylpyridinium chloride)dihydrate as in claim
 1. 5. 4,4''-carbonylbis(1-methylpyridinium tosylate) as in claim
 1. 